A series of bismuth heterocycles, termed bismoles, were synthesized via the efficient metallacycle transfer (Bi/Zr exchange) involving readily accessible zirconacycles. The luminescence properties of three structurally distinct bismoles were explored in detail via time-integrated and time-resolved photoluminescence spectroscopy using ultrafast laser excitation. Moreover, time-dependent density functional theory computations were used to interpret the nature of fluorescence versus phosphorescence in these bismuth-containing heterocycles and to guide the future preparation of luminescent materials containing heavy inorganic elements. Specifically, orbital character at bismuth within excited states is an important factor for achieving enhanced spin–orbit coupling and to promote phosphorescence. The low aromaticity of the bismole rings was demonstrated by formation of a CuCl π-complex, and the nature of the alkene-CuCl interaction was probed by real-space bonding indicators derived from Atoms-In-Molecules, the Electron Localizability Indicator, and the Non-Covalent Interaction index; such tools are of great value in interpreting nonstandard bonding environments within inorganic compounds.

中文翻译：

---

理解铋中磷光的起源：合成与计算研究

通过涉及容易获得的氧化锆环的有效金属环转移（Bi / Zr交换）合成了一系列称为双摩尔的铋杂环。通过使用超快激光激发的时间积分和时间分辨光致发光光谱学，详细研究了三种结构不同的双分子的发光特性。此外，依赖于时间的密度泛函理论计算可用于解释这些含铋杂环中荧光与磷光的本质，并指导将来制备含重无机元素的发光材料。具体而言，在激发态下铋的轨道特性是实现增强的自旋-轨道耦合和促进磷光的重要因素。通过形成CuClπ络合物证明了铋环的低芳香性，并通过衍生自原子内分子的实空间键合指示剂，电子定位性指示剂和碳原子探测了烯烃-CuCl相互作用的性质。非共价相互作用指数；这样的工具在解释无机化合物中的非标准键合环境方面具有重要价值。